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In order to model the fate and transport of particles following a nuclear explosion, there must first be an understanding of individual physical and chemical processes that affect particle formation. One interaction pertinent to fireball chemistry and resultant debris formation is that between uranium and oxygen. In this study, we use laser ablation of uranium metal in different concentrations of oxygen gas, either

Energetic events such as meteorite impacts or nuclear explosions in silicate-rich environments produce compositionally heterogeneous melts/vapors that quench to glasses such as tektites and fallout. These glassy byproducts constitute a compositional record of an unknown vapor combined with melted, compositionally heterogeneous environmental materials. The energetic formation process often results in incomplete mixing in the melt, being preserved as a glass. While this chemical heterogeneity can theoretically be interpreted to understand the starting conditions of the system, individual source materials may have overlapping element abundances and chemical behaviors that complicate interpretation using tools such as bivariate analysis. This paper develops and compares multivariate linear-least squares approaches to understand major element relationships in compositionally heterogeneous glasses. We compare classical least squares (CLS) and principal component analysis (PCA) with two multivariate curve resolution–alternating least squares (MCR-ALS) optimization techniques that are novel in application. These approaches are tested using synthetic data to understand sensitivities to the resulting determination of the abundances and compositions of the precursor components. We explore the impact of incomplete a priori knowledge of the system prior to an energetic glass formation event on the resulting confidence and accuracy of the modeled solution (i.e., the number, composition, and abundances of the precursor materials). We conclude that a closure and equality constrained MCR-ALS approach is the most robust means of identifying precursor components, and is a suitable alternative to CLS-style approaches when the investigator has incomplete knowledge of the starting precursor chemical compositions. The MCR-ALS approach is then applied to measurements of fallout glass reported in the literature, demonstrating how multivariate approaches can be applied to objectively establish pre-event source term compositions and contributions.

Recently acquired high-resolution images of nanosecond laser ablation plumes suggest a strong correlation between the internal plume structure and the type of material being ablated. However, the details of this relation are currently not well understood. In this work, we attempt to explore this correlation using a 2D radiation hydrodynamics model to study the dependence of internal plume structure formation on the ablation material. Spatio-temporal emission maps and plume expansion velocities from experimental measurements are compared with the model predictions, including synthetic emission maps. The shape and expansion rate of an outer air plume region are found to be in good agreement for both carbon and aluminum, as are the inner material plume dynamics for carbon ablation. The largest disagreement is observed in the case of a polished aluminum target, where the chaotic inner plume features seen in the experimental images are not observed in the model. The possible physical mechanisms responsible for this discrepancy are discussed. This effort constitutes a continued development toward a predictive model of ablation plume dynamics and chemistry for various materials in extreme environments.

Above-ground nuclear explosions that interact with the surface of the earth entrain materials from the surrounding environment, influencing the resulting physical and chemical evolution of the fireball, which can affect the final chemical phase and mobility of hazardous radionuclides that are dispersed in the environment as fallout particles. The interaction of iron with a nuclear explosion is of specific interest due to the potential for iron to act as a redox buffer and because of the likelihood of significant masses of metals to be present in urban environments. We investigated fallout from a historic surface interacting nuclear explosion conducted on a steel tower and report the discovery of widespread and diverse iron-rich micro-structures preserved within the samples, including crystalline dendrites and micron-scale iron-rich spheres with liquid immiscibility textures. We assert these micro-structures reflect local redox conditions and cooling rates and can inform interpretation of high temperature events, enabling new insights into fireball condensation physics and chemistry when metals from the local environment (i.e. structural steel) are vaporized or entrained. These observations also significantly expand the availability of silicate immiscibility datasets applicable to rapidly quenched systems such as meteorite impact melt glass.

Renewed interest in gallium isotope systematics has stemmed from the fact that Ga is moderately volatile and is hypothesized to undergo kinetic fractionation during evaporation. Here, we present the first Ga isotope data from terrestrial volatile depleted samples including a suite of experimentally heated rhyolitic soils, fallout melt glass, and splash-form tektites from the Australasian strewn field (hereafter termed australite tektites). The Ga in these samples is isotopically heavy compared to Ga in terrestrial basalts and estimates for the composition of the bulk silicate Earth (BSE). For each sample suite the isotopic fractionation of Ga scales with the degree of Ga depletion, consistent with isotopic fractionation caused by evaporation. The rapid experimental heating of rhyolitic soil to temperatures ranging between 1600 and 2200 °C resulted in volatile loss from the starting soil. Based on the fraction of Ga that was evaporated and the degree of Ga isotopic fractionation between starting soil and experimental samples, we calculate a fractionation factor (α) of 0.99891 ± 0.00024. This is within uncertainty of the fractionation factor we previously calculated for Zn isotopes in the same sample suite (0.99879 ± 0.00013). Although Ga isotopic data from nuclear fallout melt glass is less coherent, the Ga isotope systematics are generally consistent with a suppressed fractionation factor of approximately 0.9995–0.9998 during evaporation, which is also similar to the behavior of Zn systematics. Thus, although the fractionation factors obtained from the laser heating experiments and fallout melt glass are different, in both cases Ga and Zn behave similarly, as evidenced by the covariation of δ71Ga and δ66Zn in these samples. The behavior of Ga isotopes in australite tektites is more difficult to constrain because we do not know the location of the impact site and hence the chemical composition of the target rocks. Nevertheless, based on the composition of more volatile rich Muong-Nong type tektites, we estimate that evaporative fractionation of Ga occurs with an α between 0.9998 and 0.9987; broadly consistent with data from the laser heating experiments and nuclear fallout glass. There is no correlation between δ71Ga and δ66Zn values in australite tektites which is likely to reflect inherited isotopic heterogeneity from weathered precursor material in combination with varying extents of evaporative loss during tektite formation. Gallium isotope ratios in mare basalts are generally isotopically heavy compared to basalts from Earth. Individual mare basalts have δ71Ga and δ66Zn values that do not correlate, contrary to data from the laser levitation experiments and nuclear fallout glass. This suggests that δ71Ga and/or δ66Zn values were fractionated by geologic processes after the Moon had accreted.

The predictive models that describe the fate and transport of radioactive materials in the atmosphere following a nuclear incident (explosion or reactor accident) assume that uranium-bearing particulates would attain chemical equilibrium during vapor condensation. In this study, we show that kinetically driven processes in a system of rapidly decreasing temperature can result in substantial deviations from chemical equilibrium. This can cause uranium to condense out in oxidation states (e.g., UO3 vs UO2) that have different vapor pressures, significantly affecting uranium transport. To demonstrate this, we synthesized uranium oxide nanoparticles using a flow reactor under controlled conditions of temperature, pressure, and oxygen concentration. The atomized chemical reactants passing through an inductively coupled plasma cool from ∼5000 to 1000 K within milliseconds and form nanoparticles inside a flow reactor. The ex situ analysis of particulates by transmission electron microscopy revealed 2-10 nm crystallites of fcc-UO2 or α-UO3 depending on the amount of oxygen in the system. α-UO3 is the least thermodynamically preferred polymorph of UO3. The absence of stable uranium oxides with intermediate stoichiometries (e.g., U3O8) and sensitivity of the uranium oxidation states to local redox conditions highlight the importance of in situ measurements at high temperatures. Therefore, we developed a laser-based diagnostic to detect uranium oxide particles as they are formed inside the flow reactor. Our in situ measurements allowed us to quantify the changes in the number densities of the uranium oxide nanoparticles (e.g., UO3) as a function of oxygen gas concentration. Our results indicate that uranium can prefer to be in metastable crystal forms (i.e., α-UO3) that have higher vapor pressures than the refractory form (i.e., UO2) depending on the oxygen abundance in the surrounding environment. This demonstrates that the equilibrium processes may not dominate during rapid condensation processes, and thus kinetic models are required to fully describe uranium transport subsequent to nuclear incidents.

The 238U decay constant (λU-238) is fundamental to radioisotope-based chronometry in the Earth and planetary sciences, yet only a single published λU-238 value (Jaffey et al. in Phys Rev C 4(5):1889–1906, 1971) is widely applied. We have determined λU-238 via the novel approach of measuring of 234Th ingrowth in high-purity 238U solutions, using isotope dilution mass spectrometry (ID-MS). The 234Th decay constant (λTh-234) was measured via decay counting with high-purity Ge (HPGe) γ detectors. Preliminary results for λU-238 agree with the value determined by α-counting [1] within the elevated uncertainty of 0.462% (k = 2). Ongoing efforts to reproduce λU-238 with reduced experimental uncertainties will inform future conclusions.

Aerodynamically-shaped glassy fallout is formed when vapor phase constituents from the nuclear device are incorporated into molten carriers (i.e. fallout precursor materials derived from soil or other near-field environmental debris). The effects of speciation and diffusive transport of condensing constituents are not well defined in models of fallout formation. Previously we reported observations of diffuse micrometer scale layers enriched in Na, Fe, Ca, and 235U, and depleted in Al and Ti, at the interfaces of agglomerated fallout objects. Here, we derive the timescales of uranium mass transport in such fallout as it cools from 2500 K to 1500 K by applying a 1-dimensional planar diffusion model to the observed 235U/30Si variation at the interfaces. By modeling the thermal transport between the fireball and the carrier materials, the time of mass transport is calculated to be

In this work, several individual grains of uranium minerals—uraninite with high content of Ca, Ca-rich boltwoodite, growths of uranophane with β-uranophane, and weeksite—from different uranium deposits were studied by a scanning nuclear microprobe. Particle-induced X-ray emission technique provided by the microprobe (µ-PIXE) was carried out to obtain a concentration and 2D distribution of elements in these minerals. In addition, energy dispersive X-ray spectrometry (SEM-EDS) provided by a scanning electron microscope was used. The types of minerals were determined by X-ray diffraction methods. Results of this study improved the understanding of trace elemental composition of the uranium minerals depending on their origin. Obtained signatures could be linked then to the sample provenance. Such data are important for nuclear forensics to identify the ore types and even specific ore bodies, when only small samples may be available for analysis. In this study, the µ-PIXE technique was used for obtaining the 2D distribution of trace elements that are not commonly measured by SEM-EDS at the relevant concentrations. The detected levels and precisions of elements determination by µ-PIXE were also defined. Using µ-PIXE, several micro mineral inclusions such as phosphate with high level of V and Si were identified. The age of the uranium minerals was estimated due to a significant content of radiogenic Pb that provides an additional parameter for determination of the main attributive characteristics of the minerals. This work also showed that due to its high elemental sensitivity the nuclear microprobe can be a new analytical tool for creating a nuclear forensic database from the known uranium deposits and a subsequent analysis of the intercepted illicit materials.

Zinc isotopes fractionate during evaporation, and thus can potentially be used to calculate the proportion of volatile elemental loss from objects such as tektites, nuclear fallout melt glasses formed from silicate soils, and rocks from the Moon. The utility of the Zn isotope system in constraining the magnitude of volatile loss depends on accurate knowledge of its fractionation behavior during evaporation, i.e., the Zn isotope fractionation factor. Here, we present new results of Zn isotope analyses of experimentally heated soil samples, together with analyses of environmentally derived fallout melt glasses, and australite tektites, to better constrain how and to what extent Zn isotopes fractionate during thermally-driven evaporation. Major and trace element analyses of melt glass derived from the experimental heating of rhyolitic and arkosic soils demonstrates that elemental fractionation progressively becomes more important with increasing temperature and time. Initial Zn isotope ratios in the rhyolitic and arkosic soils are similar to upper continental crustal (UCC) values but become increasingly isotopically heavy as more Zn is lost from the heated glass, with a maximum δ66Zn value of +1.49 ± 0.05‰. The progressive loss of Zn from the rhyolitic soil is consistent with a fractionation factor (α) of 0.99879 ± 13. After loss of a labile component from the arkosic soil further evaporative loss of Zn from the silicate rich residue is also consistent with an α of ∼0.9988. This fractionation factor is not sensitive to either the heating temperature or duration. The fallout melt glass, derived from near surface nuclear weapons tests, and natural tektite samples are both relatively enriched in isotopically heavy Zn compared to the UCC. Although the fallout melt glass is largely comprised of the same rhyolitic soil used in our experiments the extent of Zn isotope fractionation is lower; consistent with an α of 0.9997. This is similar to estimated values of α associated with loss of Zn from Trinitite and lunar rocks. It is more difficult to constrain a value for α from australite tektites because the location of the impact site is not well constrained. Based on our analyses, we estimate a range of α values between 0.9988 and 0.9997, which is broadly consistent with experimental data and analyses of fallout melt glass. In all cases the measured Zn isotope fractionation factors are much lower than would be expected from evaporative loss of Zn in a high vacuum. We hypothesize that, for Zn, the value of α is dependent on the localized gas pressure and composition, with the degree of isotopic fractionation decreasing from high vacuum (

Nuclear forensic science seeks to identify the origin of nuclear materials found outside regulatory control. It is increasingly recognized as an integral part of a robust nuclear security program. This review highlights areas of active, evolving research in nuclear forensics, with a focus on analytical techniques commonly employed in Earth and planetary sciences. Applications of nuclear forensics to uranium ore concentrates (UOCs) are discussed first. UOCs have become an attractive target for nuclear forensic researchers because of the richness in impurities compared to materials produced later in the fuel cycle. The development of chronometric methods for age dating nuclear materials is then discussed, with an emphasis on improvements in accuracy that have been gained from measurements of multiple radioisotopic systems. Finally, papers that report on casework are reviewed, to provide a window into current scientific practice.

Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process between uranium atoms and potential isobars without the aid of chemical purification and separation. The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of the 235U/238U ratio to decrease laser-induced isotopic fractionation. In application, isotope standards are used to identify and correct bias in measured isotope ratios, but understanding laser-induced bias from first-principles can improve the precision and accuracy of experimental measurements. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variations in laser parameters on the measured isotope ratio. The model uses atomic data and empirical descriptions of laser performance to estimate the laser-induced bias expected in experimental measurements of the 235U/238U ratio. Empirical corrections are also included to account for ionization processes that are difficult to calculate from first principles with the available atomic data. Development of this model has highlighted several important considerations for properly interpreting experimental results.

Five silicate fallout glass spherules produced in a uranium-fueled, near-surface nuclear test were characterized by secondary ion mass spectrometry, electron probe microanalysis, autoradiography, scanning electron microscopy, and energy-dispersive x-ray spectroscopy. Several samples display compositional heterogeneity suggestive of incomplete mixing between major elements and natural U ((238)U/(235)U = 0.00725) and enriched U. Samples exhibit extreme spatial heterogeneity in U isotopic composition with 0.02 < (235)U/(238)U < 11.84 among all five spherules and 0.02 < (235)U/(238)U < 7.41 within a single spherule. In two spherules, the (235)U/(238)U ratio is correlated with changes in major element composition, suggesting the agglomeration of chemically and isotopically distinct molten precursors. Two samples are nearly homogenous with respect to major element and uranium isotopic composition, suggesting extensive mixing possibly due to experiencing higher temperatures or residing longer in the fireball. Linear correlations between (234)U/(238)U, (235)U/(238)U, and (236)U/(238)U ratios are consistent with a two-component mixing model, which is used to illustrate the extent of mixing between natural and enriched U end members.

Nuclear forensic analysis was conducted on two uranium samples confiscated during a police investigation in Victoria, Australia. The first sample, designated NSR-F-270409-1, was a depleted uranium powder of moderate purity (∼ 1000 μg/g total elemental impurities). The chemical form of the uranium was a compound similar to K2(UO2)3O4 · 4H2O. While aliquoting NSR-F-270409-1 for analysis, the body and head of a Tineid moth was discovered in the sample. The second sample, designated NSR-F-270409-2, was also a depleted uranium powder. It was of reasonably high purity (∼ 380 μg/g total elemental impurities). The chemical form of the uranium was primarily UO3 · 2H2O, with minor phases of U3O8 and UO2. While aliquoting NSR-F-270409-2 for analysis, a metal staple of unknown origin was discovered in the sample. The presence of 236U and 232U in both samples indicates that the uranium feed stocks for these samples experienced a neutron flux at some point in their history. The reactor burn-up calculated from the isotopic composition of the uranium is consistent with that of spent fuel from natural uranium (NU) fueled Pu production. These nuclear forensic conclusions allow us to categorically exclude Australia as the origin of the material and greatly reduce the number of candidate sources.

Modern autoradiography techniques based on phosphorimaging technology using image plates (IPs) and digital scanning can identify heterogeneities in activity distributions and reveal material properties, serving to inform subsequent analyses. Here, we have adopted these advantages for applications in nuclear forensics, the technical analysis of radioactive or nuclear materials found outside of legal control to provide data related to provenance, production history, and trafficking route for the materials. IP autoradiography is a relatively simple, non-destructive method for sample characterization that records an image reflecting the relative intensity of alpha and beta emissions from a two-dimensional surface. Such data are complementary to information gathered from radiochemical characterization via bulk counting techniques, and can guide the application of other spatially resolved techniques such as scanning electron microscopy (SEM) and secondary ion mass spectrometry (SIMS). IP autoradiography can image large 2-dimenstional areas (up to 20×40cm), with relatively low detection limits for actinides and other radioactive nuclides, and sensitivity to a wide dynamic range (105) of activity density in a single image. Distributions of radioactivity in nuclear materials can be generated with a spatial resolution of approximately 50μm using IP autoradiography and digital scanning. While the finest grain silver halide films still provide the best possible resolution (down to ∼10μm), IP autoradiography has distinct practical advantages such as shorter exposure times, no chemical post-processing, reusability, rapid plate scanning, and automated image digitization. Sample preparation requirements are minimal, and the analytical method does not consume or alter the sample. These advantages make IP autoradiography ideal for routine screening of nuclear materials, and for the identification of areas of interest for subsequent micro-characterization methods. In this paper we present a summary of our setup, as modified for nuclear forensic sample analysis and related research, and provide examples of data from select samples from the nuclear fuel cycle and historical nuclear test debris.

Nuclear weapons represent one of the most immediate threats of mass destruction. In the event that a procured or developed nuclear weapon is detonated in a populated metropolitan area, timely and accurate nuclear forensic analysis and fallout modeling would be needed to support attribution efforts and hazard assessments. Here we demonstrate that fissiogenic xenon isotopes retained in radioactive fallout generated by a nuclear explosion provide unique constraints on (1) the timescale of fallout formation, (2) chemical fractionation that occurs when fission products and nuclear fuel are incorporated into fallout, and (3) the speciation of fission products in the fireball. Our data suggest that, in near surface nuclear tests, the presence of a significant quantity of metal in a device assembly, combined with a short time allowed for mixing with the ambient atmosphere (seconds), may prevent complete oxidation of fission products prior to their incorporation into fallout. Xenon isotopes thus provide a window into the chemical composition of the fireball in the seconds that follow a nuclear explosion, thereby improving our understanding of the physical and thermo-chemical conditions under which fallout forms.

We present major element and actinide composition data from a population of fallout glass samples produced from a single near-surface nuclear detonation. Glass major element compositions indicate that composition of local geology is a primary control on bulk fallout chemical composition. Uranium isotope compositions indicate that vaporized, residual fuel was incorporated into the melts prior to solidification, likely within seconds, and are consistent with two-component mixing between naturally-occurring uranium and residual uranium fuel. Model ages of the residual fuel in fallout are systematically inaccurate, biased towards older ages, and are consistent with two-component mixing between naturally-occurring daughter nuclides in local sediment and decay-derived daughter nuclides from residual nuclear fuel. Multiple processes such as mixing, agglomeration of melted sediment-derived droplets, and incorporation of condensates must all occur within the timescale between sediment melting and melt solidification.

Magnesium and silicon isotopic profiles across melilite grains in two type B1 and two type B2 calcium-aluminum-rich inclusions (CAIs) reveal differing but constant enrichments in heavy isotopes everywhere except ≤1000 lm from the CAI margins. There is no close correlation in the B1s or the B2s between isotopic composition and akermanite content of the melilite, a measure of progressive igneous crystallization, yet such a correlation might be expected in a type B2: without a melilite mantle (as in B1s) to seal the interior off and prevent further evaporation, the melt would have maintained communication with the external gas. These observations indicate a model in which B1s and B2s solidified under differing conditions. The B2s solidified under lower hydrogen pressures (PH2 ≤ 10 � 4 - 10 � 5 bars) than did B1s (PH2 > 10 � 4 bars), so surface volatilization was slower in the B2s and internal chemical and isotopic equilibrium was maintained over the interval of melilite crystallization. The outermost zones of the CAIs (≤1000 lm from the edge) are not consistently enriched in heavy isotopes relative to the interiors, as might be expected from diffusion-limited surface evaporation of the melt. In all cases, the magnesium in the CAI margins is lighter than in the interiors. In one case, silicon in the margin also is lighter, but locally in some CAIs, it is isotopically heavier near the surface. If melt evaporation played a role in the formation of these outer zones, a later event in many cases caused isotopic re-equilibration with an external and isotopically near-normal reservoir.

This study combines electron microscopy equipped with energy dispersive spectroscopy to probe major element composition and autoradiography to map plutonium in order to examine the spatial relationships between plutonium and fallout composition in aerodynamic glassy fallout from a nuclear weapon test. A sample set of 48 individual fallout specimens were interrogated to reveal that the significant chemical heterogeneity of this sample set could be described compositionally with a relatively small number of compositional endmembers. Furthermore, high concentrations of plutonium were never associated with several endmember compositions and concentrated with the so-called mafic glass endmember. This result suggests that it is the physical characteristics of the compositional endmembers and not the chemical characteristics of the individual component elements that govern the un-burnt plutonium distribution with respect to major element composition in fallout.

Resonance ionization mass spectrometry was used to measure the composition of the sputtered flux from 15 keV Ga+, Au+, Au2 + and Au3 + primary ions impacting a 235U enriched U3O8 standard. We demonstrate that molecular fragmentation decreases as the primary ion mass and nuclearity increases. Stopping and range of ions in matter calculations show that cluster ions (Au2 + and Au3 +) deposit more of their energy via direct knock-ons with near-surface target atoms, whereas monatomic ions (Ga+ and Au+) penetrate much deeper into the target sub-surface region. We correlate these results to the experimental observations by showing that increased cluster ion sputter yields partition the projectile energy over a larger number of sputtered molecules. Therefore, while cluster ions deposit more total energy into the near surface region of the target compared to monatomic ions, the energy per molecule decreases with projectile mass and nuclearity. Less energy per molecule decreases the number of U–O bond breaks and, consequently, leads to a decrease in molecular fragmentation. Additionally, the extent of molecular fragmentation as a function of ion dose was evaluated. We show that molecular fragmentation increases with increased ion dose; primarily as a result of sub-surface chemical damage accumulation. The relative intensity of this effect appears to be projectile independent.

High precision SIMS 26 Al- 26 Mg isotope analyses were performed for a pristine Type B1 CAI Leoville 3535-1 on multiple mineral phases that include aluminum-rich zoned melilite mantle (Ak20-Ak60), magnesium-rich melilite (Ak70), fassaite, spinel and anorthite in the core. The data yield a well-defined internal isochron with an inferred initial 26 Al/ 27 Al ratio of (5.002 ± 0.065) � 10 � 5 , which is lower than those of bulk CAIs and pristine fine-grained CAIs. Assuming homogeneous dis- tribution of 26 Al in the early solar system, Leoville 3535-1 formed � 50 ka after the time corresponding to the bulk CAI iso- chron. One anorthite analysis near the grain boundary adjacent to melilite shows sub-lm-scale heterogeneous magnesium distribution, though the 26 Al- 26 Mg data plot on the isochron regression. Thus, the internal 26 Al- 26 Mg system of the CAI remained closed since the last melting event that crystallized anorthite. High precision magnesium isotope analyses of magnesium-rich minerals (fassaite, magnesium-rich melilite, and spinel) show a small amount of scatter from the regression line (� 0.1&) beyond analytical uncertainties. Most spinel and some fassa- ite data are systematically displaced below and above the regression line, respectively. It is likely that spinel remained unmelted at the time of the last melting event, while fassaite and anorthite crystallized from a partial melt. The regression line made by fassaite and anorthite data shows an initial 26 Al/ 27 Al ratio indistinguishable from that using all data. Mass dependent fractionation of magnesium isotopes in spinel is the same as those in melilite and fassaite (d 25 Mg � 5&), indicating that magnesium isotope fractionation, presumably from evaporative magnesium loss, predated the last melting event. Thus a majority of the CAI appears to have escaped magnesium isotope exchange with nebular gas during the last melting event, except for the outer rim of the melilite mantle that shows slightly lower d 25 Mg values. The 26 Al- 26 Mg systematics of this Leoville Type B CAI suggest it experienced a final melting event at � 50 ka after the initial Al-Mg fractionation event. This may correspond to melting during the active protostar stage (known as "Class I"), during which sporadic high temperature heating events repeatedly affected refractory solids in the solar nebula. 2012 Elsevier Ltd. All rights reserved.

The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of {sup 235}U/{sup 238}U ratios by resonance ionization mass spectrometry (RIMS) to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a three-color, three-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from 10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation.

Resonance ionization mass spectrometry offers extremely high sensitivity and elemental selectivity in microanalysis, but the isotopic precision attainable by this technique has been limited. Measured isotope ratios are sensitive to small fluctuations in the pointing, pulse timing, and wavelength of the resonance lasers. We show that, by minimizing these fluctuations using feedback controls and by power-broadening the optical transitions, we are able to measure chromium isotope ratios with statistics-limited precision better than 1%. Small additional improvements in reproducibility come from careful shaping of the electric field in the region where atoms are photoionized and from minimizing pulse-to-pulse variations in the time-of-flight mass spectrometer through which the photoions travel. The increased reproducibility of isotopic measurements on standard materials has enabled us to detect anomalous chromium isotopic abundances in presolar SiC grains extracted from primitive meteorites.

Calcium-, aluminum-rich inclusions (CAIs) are often enriched in the heavy isotopes of magnesium and silicon relative to bulk solar system materials. It is likely that these isotopic enrichments resulted from evaporative mass loss of magnesium and silicon from early solar system condensates while they were molten during one or more high-temperature reheating events. Quantitative interpretation of these enrichments requires laboratory determinations of the evaporation kinetics and associated isotopic fractionation effects for these elements. The experimental data for the kinetics of evaporation of magnesium and silicon and the evaporative isotopic fractionation of magnesium is reasonably complete for Type B CAI liquids (Richter F. M., Davis A. M., Ebel D. S., and Hashimoto A. (2002) Elemental and isotopic fractionation of Type B CAIs: experiments, theoretical considerations, and constraints on their thermal evolution. Geochim. Cosmochim. Acta66, 521–540; Richter F. M., Janney P. E., Mendybaev R. A., Davis A. M., and Wadhwa M. (2007a) Elemental and isotopic fractionation of Type B CAI-like liquids by evaporation. Geochim. Cosmochim. Acta71, 5544–5564.). However, the isotopic fractionation factor for silicon evaporating from such liquids has not been as extensively studied. Here we report new ion microprobe silicon isotopic measurements of residual glass from partial evaporation of Type B CAI liquids into vacuum. The silicon isotopic fractionation is reported as a kinetic fractionation factor, αSi, corresponding to the ratio of the silicon isotopic composition of the evaporation flux to that of the residual silicate liquid. For CAI-like melts, we find that αSi = 0.98985 ± 0.00044 (2σ) for 29Si/28Si with no resolvable variation with temperature over the temperature range of the experiments, 1600–1900 °C. This value is different from what has been reported for evaporation of liquid Mg2SiO4 (Davis A. M., Hashimoto A., Clayton R. N., and Mayeda T. K. (1990) Isotope mass fractionation during evaporation of Mg2SiO4. Nature347, 655–658.) and of a melt with CI chondritic proportions of the major elements (Wang J., Davis A. M., Clayton R. N., Mayeda T. K., and Hashimoto A. (2001) Chemical and isotopic fractionation during the evaporation of the FeO–MgO–SiO2–CaO–Al2O3–TiO2–REE melt system. Geochim. Cosmochim. Acta65, 479–494.). There appears to be some compositional control on αSi, whereas no compositional effects have been reported for αMg. We use the values of αSi and αMg, to calculate the chemical compositions of the unevaporated precursors of a number of isotopically fractionated CAIs from CV chondrites whose chemical compositions and magnesium and silicon isotopic compositions have been previously measured.

On Monday 20 July, Caterina Fox, Ruth Kips and Kim Knight were invited to participate in Kazakhstan's nuclear material inventory management working group meeting coordinated by Alexander Vasilliev as nuclear forensics subject matter experts. The meeting included participants from Kazakhstan's nuclear regulatory agency (CAESC, the Committee on Atomic and Energetic Supervision and Control) and 3 institutes 1. Institute of Nuclear Physics, INP (Almaty), 2. National Nuclear Center, NNC (Kurchatov), and 3. Ulba Metallurgical Plant, UMP (Oskemen). CAESC requested attendance of an MC&A expert, an IT Specialist, and a Physical Security Specialist from each site. The general meeting concerned considerations for creating unified or compatible systems for nuclear material inventory management. NSDD representatives provided an overview of nuclear forensics and presented considerations for developments of inventory management that might be synergistic with future consideration of development of a National Nuclear Forensics Library to support nuclear forensics investigations.

We appreciate this opportunity for further discussion of flow and field relations within the Rajahmundry Traps, and their timing relative to Deccan Trap volcanism. Knight et al., 2003a relied on simplified stratigraphic designation and nomenclature for Rajahmundry Trap flows, labeling dUpperT or dLowerT flows relative to the presence of a primary sedimentary interlayer [1]. This designation and its implication of related lava packages may not be strictly valid, as suggested by Baski (this volume), and we present further insight below. Several points of the comment [2] are based on the assumption that a single flow is present for each of the Upper and Lower Rajahmundry Trap units. Both drill hole and field observation, however, suggest otherwise. Multiple flows (as many as 8) of Rajahmundry Trap lavas assigned to both Upper and Lower units are well documented [e.g., 3–5], often occurring sandwiched between multiple sedimentary horizons above and below the thick (and thus designated as the dmainT) sedimentary interlayer. The assumption of a single flow may hold for the surface exposures of the Upper unit used in the study of [1], where flow boundaries (if present) were not possible to discern. Within Lower unit exposures, however, at least two distinct lava flows were observed and sampled in the field (Fig. 1), and have been reported by multiple authors from [6], to the present. Further geochemical evaluation (discussed here) supports the presence of at least three lava groups. The discussion [2] also presents a re-evaluation of our age data resulting in conclusions identical to those of [1].We stand by our published acceptance and rejection criteria for our data, as well as our quoted errors. Additional graphics relating unpublished geochemical and chronological data [2] are interesting, but cannot be properly evaluated in the absence of the inclusion of the raw data.

A new stratigraphy for bimodal Oligocene flood volcanism that forms the volcanic plateau of northern Yemen is presented based on detailed field observations, petrography and geochemical correlations. The >1 km thick volcanic pile is divided into three phases of volcanism: a main basaltic stage (31 to 29.7 Ma), a main silicic stage (29.7 to 29.5 Ma), and a stage of upper bimodal volcanism (29.5 to 27.7 Ma). Eight large-volume silicic pyroclastic eruptive units are traceable throughout northern Yemen, and some units can be correlated with silicic eruptive units in the Ethiopian Traps and to tephra layers in the Indian Ocean. The silicic units comprise pyroclastic density current and fall deposits and a caldera-collapse breccia, and they display textures that unequivocally identify them as primary pyroclastic deposits: basal vitrophyres, eutaxitic fabrics, glass shards, vitroclastic ash matrices and accretionary lapilli. Individual pyroclastic eruptions have preserved on-land volumes of up to ∼850 km3. The largest units have associated co-ignimbrite plume ash fall deposits with dispersal areas >1×107 km2 and estimated maximum total volumes of up to 5,000 km3, which provide accurate and precisely dated marker horizons that can be used to link litho-, bio- and magnetostratigraphy studies. There is a marked change in eruption style of silicic units with time, from initial large-volume explosive pyroclastic eruptions producing ignimbrites and near-globally distributed tuffs, to smaller volume (

A combined paleomagnetic and Ar-40/Ar-39 study was carried out along eight stratigraphically overlapping sections in the Oligocene Afro-Arabian flood volcanic province in Yemen (73 sites). The composite section covers the entire volcanic stratigraphy in the sampling region and represents five polarity zones that are correlated to the geomagnetic polarity time scale based on Ar-40/Ar-39 ages from this and previous studies. The resulting magnetostratigraphy is similar to that of the conjugate margin in Ethiopia. The earliest basaltic volcanism took place in a reverse polarity chron that appears to correspond to C11r, while the massive rhyolitic ignimbrite eruptions correlated to ash layers in Oligocene Indian Ocean sediment 2700 km away from the Afro-Arabian traps, appear to have taken place during magnetochron C11n. The youngest ignimbrite was emplaced during magnetochron C9n. Both 40Ar/39Ar and paleornagnetic data suggest rapid < 1 Ma eruption of the basal basalt units and punctuated eruption of the upper silicic units over a duration potentially as long as 3 Ma with interspersed eruptive hiatuses. Eruption of the basal basalts may have preceded the Oi2 cooling event. The paleornagnetic pole lambda=74.2 degrees N, phi=249.1 degrees E (A95=3.6 degrees; N=48) is supported by a positive reversal test. Paleosecular variation, estimated as the angular standard deviation of the VGP distribution 14.2 degrees+2.3 degrees/-1.7 degrees, is close to expected, suggesting that the paleornagnetic pole represents a time-averaged field. The pole is in excellent accord with the paleornagnetic poles obtained from the Ethiopian part of the Afro-Arabian province, after closure of the Red Sea. By analyzing Afro-Arabian paleomagnetic data in conjunction with contemporaneous paleomagnetic poles available from different latitudes we argue that the Oligocene paleomagnetic field was dominated by the axial dipole with insignificant non-dipole field contributions. (Less)

Rajahmundry lava flows exposed along India’s eastern coast have long been suggested to be outliers of the more massive Deccan Traps despite the distance of more than 400 km separating their present-day erosional remnants. Recent rock quarries in Rajahmundry Trap lavas of basaltic composition have exposed fresh surfaces available for sampling displaying clear stratigraphic relationships within the typical basalt–sediment–basalt stratigraphy. 40Ar/39Ar ages for plagioclase separates from eight Rajahmundry lavas both above (Upper Trap) and below (Lower Trap) the continuous sedimentary interlayer reveal a mean age of 64.7±0.5 Ma. Plagioclase Ca/K values are high (20–350), requiring use of finer grain sizes (63–125 μm) and well-known interference corrections for Ar isotopes produced during sample irradiation to produce the best possible ages. Individual ages confirm the rapid eruption (

We present the development of a steady state plasma flow reactor to investigate gas phase physical and chemical processes that occur at high temperature (1000 < T < 5000 K) and atmospheric pressure. The reactor consists of a glass tube that is attached to an inductively coupled argon plasma generator via an adaptor (ring flow injector). We have modeled the system using computational fluid dynamics simulations that are bounded by measured temperatures. In situ line-of-sight optical emission and absorption spectroscopy have been used to determine the structures and concentrations of molecules formed during rapid cooling of reactants after they pass through the plasma. Emission spectroscopy also enables us to determine the temperatures at which these dynamic processes occur. A sample collection probe inserted from the open end of the reactor is used to collect condensed materials and analyze them ex situ using electron microscopy. The preliminary results of two separate investigations involving the condensation of metal oxides and chemical kinetics of high-temperature gas reactions are discussed.

Extensive outpourings of basalt, and to a lesser extent rhyolite, are closely associated with continental break-up and plume–lithosphere interactions. The Gondwana supercontinent began to fragment during Early–Middle Jurassic times and was associated with the eruption of over three million km3 of dominantly basaltic magma. This intense magmatic episode is recorded in volcanic rocks of the Karoo (Africa), Ferrar (Antarctica) and Chon Aike (South America). K–Ar and Rb–Sr whole rock geochronology has consistently failed to produce reliable ages for these volcanic rocks, but in the last four years, the wider application of single grain 40Ar/39Ar and/or U–Pb geochronology has produced more robust and precise dating of the magmatism. This paper reviews the recent advances in high precision geochronology and provides a full recalibrated 40Ar/39Ar dataset. Application of these methods across the majority of the volcanic provinces indicates that approximately 80% of the volcanic rocks were erupted within a short, 3–4 Myr period at c. 182 Ma. This burst of magmatism occurred in the Karoo province at c. 183 Ma and in the Ferrar provinces at c. 180 Ma, and was dominated by mafic volcanism. This peak in volcanism is coincident with a second order mass extinction event at the end of the Pliensbachian when c. 5% of marine families were wiped out coinciding with widespread oceanic anoxia in the early Toarcian. A prolonged period of silicic volcanism occurred along the proto-Pacific margin, prior to, and during the main phase of break-up. Silicic volcanism was initially coincident with the plume related Karoo-Ferrar provinces, but continued over c. 40 Myr, associated with lithospheric extension and subduction along the proto-Pacific continental margin.

© 2016 Author(s). Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. The resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.

An experimental technique is described that combines tomography, Hadamard signal encodement, and a patented Fourier transform infrared (FT‐IR) emission/transmission (E/T) technique to perform simultaneous spatially resolved gas species and soot measurements during combustion. Tomographic analysis of line‐of‐sight FT‐IR data allows spatially resolved measurements to be made. Hadamard encodement of the tomographic sections increases the overall signal throughput, improving the signal to noise (S/N) ratio for each measurement. The Hadamard technique leads to a major simplification in the tomographic apparatus in that the scanning apparatus that would normally be required is eliminated, and focusing of the infrared light is much easier. An experiment demonstrating Hadamard data processing as applied to FT‐IR tomography is described. Deconvolution of the encoded data is shown to be accurate and gives the predicted improvement in S/N ratio. The FT‐IR Hadamard tomography is performed to measure soot in a fuel‐ri...

a Dipartimento di Geoscienze, Universita di Padova, and IGG-CNR, via Giotto 1, 35100-Padova, Italy b Laboratoire des Sciences de la Terre, UMR-CNRS 5570, Ecole Normale Superieure de Lyon, and UCBL, 46, Allee d'Italie, 69364 Lyon, France c Department of the Geophysical Sciences, 5734 S. Ellis Ave., HGS 237, University of Chicago, Chicago, IL 60637, USA d Dipartimento di Scienze della Terra, Universita di Perugia, Piazza Universita 1, 06100 Perugia, Italy e CEA-UVSQ, UMR 1572, LSCE-Orme, Orme Des Merisiers, 91191 Gif-sur-Yvette Cedex, France f Berkeley Geochronology Center, 2455 Ridge Road, CA94709 Berkeley, USA, and Department of Earth and Planetary Science, University of California, Berkeley, USA g UNSA—UMR Geosciences Azur, Parc Valrose, 06108 Nice, France h Department of Geology, Cadi Ayyad University, Boulevard Prince Moulay Abdellah, Marrakech, Morocco i Section des Sciences de la Terre, Universite de Geneve, 13 rue des Maraichers, 1205 Geneve, Switzerland

The Central Atlantic Magmatic Province (CAMP) is among the largest igneous provinces on Earth, emplaced synchronously with or just prior to the Triassic–Jurassic (T–J) boundary ca. 200 Ma. In great part due to the controversial connection between the occurrence of CAMP and the events of the T–J boundary, the demand for better constraints on the duration and eruptive chronology of this province has increased. More than 100 new 40 Ar/ 39 Ar ages have been published in the last 15 years, with more than half of these in the last 3 years. A careful review and selection of available ages, as well as the publication of 16 new ages from the Carolinas, Newark Basin (USA), French Guyana and Morocco are presented. Judicious selection yields a total of 58 accepted age determinations for CAMP magmatism, ranging from 202 to 190 Ma covering every part of the CAMP. A more complete picture develops with intrusive CAMP magmatism commencing as early as 202 Ma. Extrusive activity initiated abruptly ∼ 200 Ma, reaching peak volume and intensity around 199 Ma on the African margin. The main period of CAMP magmatism is confirmed as brief, but is suggested to consist of at least two phases over ∼ 1.5 Ma, with magmatism commencing along the Africa–North American margins and slightly later along the South American margin. Two volumetrically minor, but distinctive magmatic peaks centered at 195 and 192 Ma are mirrored in data from all three continents and highlighted by our statistical approach. Models describing rifting and thermal input and magma production on these timescales are explored. Despite significant advances in our understanding of the chronology of CAMP, more data of better quality and broader geographical coverage are needed to completely characterize the evolution of the CAMP and infer its geodynamic origin. In addition, lack of a well-defined T–J boundary age, as well as the absence of a relevant basis for comparison between U/Pb and 40 Ar/ 39 Ar data for this time period remain limiting factors to unambiguously linking CAMP in time with the events of the T–J boundary.

A report of human footprints preserved in 40,000-year-old volcanic ash near Puebla, Mexico (http://www.royalsoc.ac.uk/exhibit.asp?id=3616tip=1), was the subject of a press conference that stirred international media attention. If the claims (http://www.mexicanfootprints.co.uk) of Gonzalez et al. are valid, prevailing theories about the timing of human migration into the Americas would need significant revision. Here we show by 40Ar/39Ar dating and corroborating palaeomagnetic data that the basaltic tuff on which the purported footprints are found is 1.30+/-0.03 million years old. We conclude that either hominid migration into the Americas occurred very much earlier than previously believed, or that the features in question were not made by humans on recently erupted ash.

Neutron irradiation of samples for 40 Ar/ 39 Ar dating in a 235 U fission reactor requires error-producing corrections for the argon isotopes created from Ca, K, and, to a lesser extent, Cl. The fission spectrum includes neutrons with energies above 2–3 MeV, which are not optimal for the 39 K(n,p) 39 Ar reaction. These higher-energy neutrons are responsible for the largest recoil displacements, which may introduce age artifacts in the case of fine-grained samples. Both interference corrections and recoil displacements would be significantly reduced by irradiation with 2.45 MeV neutrons, which are produced by the deuteron–deuteron (D–D) fusion reaction 2 H(d,n) 3 He. A new generation of D–D reactors should yield sufficiently high neutron fluxes (>10 12 n cm −2 s −1 ) to be useful for 40 Ar/ 39 Ar dating. Modeling indicates that irradiation with D–D neutrons would result in scientific benefits of improved accuracy and broader applicability to fine-grained materials. In addition, radiological safety would be improved, while both maintenance and operational costs would be reduced. Thus, development of high-flux D–D fusion reactors is a worthy goal for 40 Ar/ 39 Ar geochronology.

The evolution of life on Earth is marked by catastrophic extinction events, one of which occurred ca. 200 Ma at the transition from the Triassic Period to the Jurassic Period (Tr-J boundary), apparently contemporaneous with the eruption of the world's largest known continental igneous province, the Central Atlantic magmatic province. The temporal relationship of the Tr-J boundary and the province's volcanism is clarified by new multidisciplinary (stratigraphic, palynologic, geochronologic, paleomagnetic, geochemical) data that demonstrate that development of the Central Atlantic magmatic province straddled the Tr-J boundary and thus may have had a causal relationship with the climatic crisis and biotic turnover demarcating the boundary. © 2004 Geological Society of America

A report of human footprints preserved in 40,000-year-old volcanic ash in Mexico is challenged in an online Brief Communication Arising. Announced to the press in July this year, if true the discovery would overturn current theories on the timing of human migration to the Americas (believed to be some 30,000 years later). Argon dating and palaeomagnetic analysis show that the surface on which the prints were found is about 1.3 million years old, making it unlikely that these were human as they would then pre-date the appearance of Homo sapiens in Africa by over a million years. Arising from: R. Dalton doi: 10.1038/news050704-4 (2005)10.1038/news050704-4 A report of human footprints preserved in 40,000-year-old volcanic ash near Puebla, Mexico ( http://www.royalsoc.ac.uk/exhibit.asp?id=3616&tip=1 ), was the subject of a press conference that stirred international media attention1. If the claims ( http://www.mexicanfootprints.co.uk ) of Gonzalez et al. are valid, prevailing theories about the timing of human migration into the Americas would need significant revision. Here we show by 40Ar/39Ar dating and corroborating palaeomagnetic data that the basaltic tuff on which the purported footprints are found is 1.30±0.03 million years old. We conclude that either hominid migration into the Americas occurred very much earlier than previously believed, or that the features in question were not made by humans on recently erupted ash.

We report a study of materials recovered from a uranium-containing plasma generated by an electric arc. The device used to generate the arc is capable of sustaining temperatures of an eV or higher for up to 100 μs. Samples took the form of a 4 μm-thick U238 film deposited onto 8 pairs of 17 μm-thick Cu electrodes supported on a 25 μm-thick Kapton backing and sandwiched between glass plates. Materials recovered from the glass plates and around the electrode tips after passage of an arc were characterized using scanning and transmission electron microscopy. Recovered materials included a variety of crystalline compounds (e.g., UO2, UC2, UCu5,) as well as mixtures of uranium and amorphous glass. Most of the materials collected on the glass plates took the form of spherules having a wide range of diameters from tens of nanometers to tens of micrometers. The composition and size of the spherules depended on location, indicating different chemical and physical environments. A theoretical analysis we have carrie...